CN103232432A - 3-difluoroethoxy-4-chloropyrazole amide compound and use thereof - Google Patents
3-difluoroethoxy-4-chloropyrazole amide compound and use thereof Download PDFInfo
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- -1 3-difluoroethoxy-4-chloropyrazole amide compound Chemical class 0.000 title abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 32
- 229910052794 bromium Chemical group 0.000 claims abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 241000607479 Yersinia pestis Species 0.000 claims abstract description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 3
- 239000000460 chlorine Substances 0.000 claims description 48
- 150000001875 compounds Chemical class 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 3
- 230000000975 bioactive effect Effects 0.000 claims 1
- 230000002265 prevention Effects 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 8
- 230000000749 insecticidal effect Effects 0.000 abstract description 7
- 241000238631 Hexapoda Species 0.000 abstract description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 abstract 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 36
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 26
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000000967 suction filtration Methods 0.000 description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Substances OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 241000500437 Plutella xylostella Species 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 5
- 239000012359 Methanesulfonyl chloride Substances 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 4
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 0 Cc1cc(Cl)cc(C(NC)O)c1NC(c1cc(Br)n[n]1-c(nccc1)c1Cl)=* Chemical compound Cc1cc(Cl)cc(C(NC)O)c1NC(c1cc(Br)n[n]1-c(nccc1)c1Cl)=* 0.000 description 3
- 230000004071 biological effect Effects 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229940125797 compound 12 Drugs 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VUYQBMXVCZBVHP-UHFFFAOYSA-N 1,1-difluoroethanol Chemical compound CC(O)(F)F VUYQBMXVCZBVHP-UHFFFAOYSA-N 0.000 description 2
- WNABMWFLKQEGCP-UHFFFAOYSA-N 2-amino-3,5-dibromobenzoic acid Chemical compound NC1=C(Br)C=C(Br)C=C1C(O)=O WNABMWFLKQEGCP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- VAMXMNNIEUEQDV-UHFFFAOYSA-N methyl anthranilate Chemical compound COC(=O)C1=CC=CC=C1N VAMXMNNIEUEQDV-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 235000014347 soups Nutrition 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 1
- LWUAMROXVQLJKA-UHFFFAOYSA-N 2-amino-3-chlorobenzoic acid Chemical class NC1=C(Cl)C=CC=C1C(O)=O LWUAMROXVQLJKA-UHFFFAOYSA-N 0.000 description 1
- KOPXCQUAFDWYOE-UHFFFAOYSA-N 2-amino-5-chloro-3-methylbenzoic acid Chemical compound CC1=CC(Cl)=CC(C(O)=O)=C1N KOPXCQUAFDWYOE-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 1
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 1
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241000255777 Lepidoptera Species 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- LHMHCLYDBQOYTO-UHFFFAOYSA-N bromofluoromethane Chemical compound FCBr LHMHCLYDBQOYTO-UHFFFAOYSA-N 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 125000006006 difluoroethoxy group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000011272 standard treatment Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
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- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a 3-difluoroethoxy-4-chloropyrazole amide compound and its preparation method and use. The 3-difluoroethoxy-4-chloropyrazole amide compound is shown in a general structural formula I, wherein in the general structural formula I, R1 represents methyl, Cl or Br; R2 represents Cl or Br; R3 represents methyl, isopropyl, tertiary butyl or allyl; and R4 represents H or Cl. The 3-difluoroethoxy-4-chloropyrazole amide compound shown in the general structural formula I has excellent insecticidal activity and can be used for preventing and controlling insect pests.
Description
Technical field
The invention belongs to the agricultural insecticide field, relate to a kind of 3-difluoroethoxy-4-chlorine pyrazol acid amide compounds and application thereof.
Background technology
Adjacent formamido-benzamide compound (fish mud fourth acceptor inhibitor class) is effective sterilant of the control lepidoptera pest developed in recent years.
PCT patent application WO2003/015519 discloses following compound (KC) with insecticidal activity:
PCT patent application WO2006/023783 discloses following compound with insecticidal activity:
CN101967139A discloses following compound with insecticidal activity:
Though the compound of above-mentioned patent disclosure has certain similarity with compound of the present invention, in the prior art, 3-difluoroethoxy-4-chlorine pyrazol acid amide compounds (formula I) is not seen open as described in the present invention.
Summary of the invention
The object of the present invention is to provide 3-difluoroethoxy-4-chlorine pyrazol acid amide compounds of a kind of novel structure and preparation method thereof, it can be used for the control of agricultural or forestry harmful insect.
Technical scheme of the present invention is as follows:
A kind of 3-difluoroethoxy-4-chlorine pyrazol acid amide compounds structure is shown in general formula I:
In the formula: R
1Be selected from methyl, Cl or Br;
R
2Be selected from Cl or Br;
R
3Be selected from methyl, sec.-propyl, the tertiary butyl, allyl group;
R
4Be selected from H or Cl.
Compound of Formula I of the present invention can be by following method preparation, and each group definition is the same in the reaction formula.
Compound I I, compound III and Methanesulfonyl chloride in acetonitrile are that the acid binding agent reaction makes compound IV with the triethylamine, then and R
3NH
2Ring-opening reaction makes compound I.Example of the present invention is seen in the preparation of compound I I and III.
Table 1 has been listed structure and the physical properties of part compound of Formula I.
The structure of table 1 compound I and physical properties
| Compound I | R 1 | R 2 | R 3 | R 4 | Outward appearance | Fusing point |
| 1 | CH 3 | Cl | CH 3 | H | White powder | 223～226℃ |
| 2 | CH 3 | Cl | CH(CH 3) 2 | H | Yellow powder | 195～198℃ |
| 3 | CH 3 | Cl | CH 2CH＝CH 2 | H | Yellow powder | 191～194℃ |
| 4 | Cl | Cl | CH(CH 3) 2 | H | White powder | 214～217℃ |
| 5 | Cl | Cl | CH 3 | Cl | White powder | 205～208℃ |
| 6 | Cl | Cl | CH 2CH＝CH 2 | Cl | Yellow powder | 200～203℃ |
| 7 | Br | Br | CH 3 | H | White powder | 234～237℃ |
| 8 | Br | Br | CH 3 | Cl | White powder | 226～229℃ |
| 9 | Br | Br | CH(CH 3) 2 | Cl | White powder | 219～222℃ |
| 10 | CH 3 | Cl | CH 3 | Cl | White powder | 212～215℃ |
| 11 | CH 3 | Cl | C(CH 3) 3 | H | White powder | 205～208℃ |
| 12 | Cl | Cl | CH(CH 3) 2 | Cl | White powder | 201～204℃ |
[0024]Advantage of the present invention and positively effect: compare with known 3-bromine pyrazol acid amide compounds (KC), The compounds of this invention is introduced difluoroethoxy 3-position pyrazoles ring first, by the lipotropy of fluorine element and the hydrophilic combination of oxyethyl group, not only improved the insecticidal activity of this compounds to some insect greatly, simultaneously also be conducive to improve its interior suction conduction in plant materials, and then the whole comprehensive use properties that improves this compounds.In the novel pesticide initiative, fluorochemicals has become the important means that improves the compound biological activity and administer resistance.Thereby The compounds of this invention has low resistance risk to the insect that existing compound has produced resistance.In addition, the synthetic used difluoroethanol of The compounds of this invention has higher boiling point, and the production process easy handling has avoided existing such fluorochemicals cost high or be difficult to drawback such as operation for gas because of raw material (as Bromofluoromethane).Compare with known 3-bromine pyrazol acid amide compounds, 3-difluoroethoxy of the present invention-4-chlorine pyrazol acid amide compounds has beyond thought high insecticidal activity, and the present invention comprises that also compound of Formula I is used to control the purposes of insect pest.
The compounds of this invention can both can use separately when pest control according to actual needs, also can use with other sterilants or sterilant isoreactivity combinations of substances, to improve the comprehensive function of product.
The present invention also comprises with the insect-killing composition of compound of Formula I as active ingredient.The weight percentage of active combination is between 1-99% in this insect-killing composition.This insect-killing composition kind also comprises acceptable carrier in agricultural, the forestry.
Composition of the present invention can preparation form use.Compound of Formula I as solubilization of active ingredient be scattered in carrier or solvent in, add suitable tensio-active agent and be mixed with missible oil, suspension agent, microemulsion or wettable powder etc.
Should be clear and definite be in claim of the present invention institute restricted portion, can carry out various conversion and change.
Embodiment
Following synthetic example and the living experimental result of surveying can be used to further specify the present invention, but do not mean that restriction the present invention.
Synthetic example:
The preparation of example 1. compounds 1:
(1) 1-(3-chloropyridine-2-yl)-3-difluoroethoxy-1H-pyrazoles-5-ethyl formate is synthetic:
In the there-necked flask of 250mL, add 0.05mol (13.37g) 1-(3-chloropyridine-2-yl)-3-hydroxyl-1H-pyrazoles-5-ethyl formate (with reference to the preparation of CN102285963A method) and 0.065mol (8.97g) salt of wormwood respectively, add acetonitrile 100mL, add 0.055mol (8.80g) 2 again, 2-difluoro ethyl methane sulfonate ester (by difluoroethanol and methylsulfonyl chloride prepared in reaction), backflow 7-8h, reaction finishes, suction filtration, boil off solvent, get product 1-(3-chloropyridine-2-yl)-3-difluoroethoxy-1H-pyrazoles-5-ethyl formate 14.90g, yield 90%.。
(2) 1-(3-chloropyridine-2-yl)-3-difluoroethoxy-4-chlorine pyrazoles-5-ethyl formate is synthetic:
In the there-necked flask of 250mL, add 0.05mol (16.60g) 1-(3-chloropyridine-2-yl)-3-difluoroethoxy-1H-pyrazoles-5-ethyl formate, dissolve with the 100mL acetonitrile, stir down, low temperature slowly drips 0.075mol (10.10g) SULPHURYL CHLORIDE, dropwises normal-temperature reaction 4-5h, reaction finishes, boil off solvent and unreacted SULPHURYL CHLORIDE, obtain 1-(3-chloropyridine-2-yl)-3-difluoroethoxy-4-chlorine pyrazoles-5-ethyl formate 16.44g, yield 90%.
(3) 1-(3-chloropyridine-2-yl)-3-difluoroethoxy-4-chlorine pyrazoles-5-formic acid is synthetic:
In the there-necked flask of 250mL, add 0.05mol (18.30g) 1-(3-chloropyridine-2-yl)-3-difluoroethoxy-4-chlorine pyrazoles-5-ethyl formate, use the 50mL dissolve with ethanol, add water 50mL, add 0.075mol (3.00g) sodium hydroxide again, stirring at normal temperature 2h, reaction finishes, steam ethanol, transfer pH to 2-3 with concentrated hydrochloric acid, separate out white solid, suction filtration, washing, drying obtain 1-(3-chloropyridine-2-yl)-3-difluoroethoxy-4-chlorine pyrazoles-5-formic acid 15.38g, yield 91%.
(4) compound 1 is synthetic:
In the there-necked flask of 100mL, add 0.02mol (3.71g) 2-amino-3-methyl-5-chloro phenylformic acid and 0.02mol (6.76g) 1-(3-chloropyridine-2-yl)-3-difluoroethoxy-4-chlorine pyrazoles-5-formic acid respectively, add the 50mL acetonitrile, stir under the ice-water bath and add 0.088mol (8.89g) triethylamine, dropwise, stir 10min, slowly drip Methanesulfonyl chloride 0.44mol (5.03g) then, reaction 4h, reaction finishes, and suction filtration obtains yellow solid, washing, solid transfer in the 100mL there-necked flask, is added the 50mL acetonitrile, drip the aqueous methylamine solution of 0.04mol (1.24g) 40%, reaction 1h, reaction finishes and steams solvent, obtains compound 1 product 7.50g, yield 73%.
The preparation of example 2. compounds 7:
Synthesizing of (1) 3,5-dibromoanthranilic acid:
Add 0.05mol (15.10g) methyl o-aminobenzoate in the there-necked flask of 250mL, with the dissolving of 100mL acetic acid, drip 0.1mol (16.00g) bromine under the normal temperature, reaction 4h has a large amount of solids to separate out, suction filtration, washing.Solid transfer in the 250mL there-necked flask, is used the 50mL dissolve with ethanol, add 50mL water, add 0.075mol (3g) sodium hydroxide again, normal-temperature reaction 2h, steam ethanol, white solid is separated out in the concentrated hydrochloric acid acidifying, suction filtration, drying obtains 3,5-dibromoanthranilic acid 13.72g, yield 93%.
(2) 1-(3-chloropyridine-2-yl)-3-difluoroethoxy-4-chlorine pyrazoles-5-formic acid synthetic sees example 1.
(3) compound 7 is synthetic:
In the there-necked flask of 100mL, add 0.02mol (5.90g) 3 respectively, 5-dibromoanthranilic acid and 0.02mol (6.76g) 1-(3-chloropyridine-2-yl)-3-difluoroethoxy-4-chlorine pyrazoles-5-formic acid, add the 50mL acetonitrile, stir under the ice-water bath and add 0.088mol (8.89g) triethylamine, dropwise, stir 10min, slowly drip Methanesulfonyl chloride 0.44mol (5.04g) then, reaction 4h, reaction finishes, suction filtration, obtain yellow solid, washing adds the 50mL acetonitrile with solid transfer in the 100mL there-necked flask, drip the aqueous methylamine solution of 0.4mol (1.24g) 40%, reaction 1h, reaction finishes and steams solvent, obtains compound 7 product 8.79g, yield 70%.
Synthesizing of example 3. compounds 12:
(1) 1-(3,5-dichloropyridine-2-yl)-3-difluoroethoxy-4-chlorine pyrazoles-5-ethyl formate is synthetic:
In the there-necked flask of 250mL, add 0.05mol (15.20g) 1-(3 respectively, 5-dichloropyridine-2-yl)-and 3-hydroxyl-1H-pyrazoles-5-ethyl formate and 0.065mol (8.97g) salt of wormwood, add acetonitrile 100mL, add 0.055mol (8.80g) 2 again, 2-difluoro ethyl methane sulfonate ester, backflow 10-11h, reaction finishes, suction filtration, boil off solvent, obtain 1-(3,5-dichloropyridine-2-yl)-3-difluoroethoxy-1H-pyrazoles-5-ethyl formate 15.55g, yield 85%.
(2) 1-(3,5-dichloropyridine-2-yl)-3-difluoroethoxy-4-chlorine pyrazoles-5-ethyl formate is synthetic:
In the there-necked flask of 250mL, add 0.05mol (18.30g) 1-(3,5-dichloropyridine-2-yl)-and 3-difluoroethoxy-1H-pyrazoles-5-ethyl formate, with the dissolving of 100mL acetonitrile, stir down, low temperature slowly drips 0.075mol (10.12g) SULPHURYL CHLORIDE, dropwise, normal-temperature reaction 4-5h, reaction finishes, boil off solvent and unreacted SULPHURYL CHLORIDE, obtain 1-(3,5-dichloropyridine-2-yl)-3-difluoroethoxy-4-chlorine pyrazoles-5-ethyl formate 17.62g, yield 88%.
(3) 1-(3,5-dichloropyridine-2-yl)-3-difluoroethoxy-4-chlorine pyrazoles-5-formic acid is synthetic:
In the there-necked flask of 250mL, add 0.05mol (20.00g) 1-(3,5-dichloropyridine-2-yl)-3-difluoroethoxy-4-chlorine pyrazoles-5-ethyl formate, use the 50mL dissolve with ethanol, add water 50mL, add 0.075mol (3g) sodium hydroxide again, stirring at normal temperature 2h, reaction finishes, steam ethanol, transfer pH to 2-3 with concentrated hydrochloric acid, separate out white solid, suction filtration, washing, drying obtain 1-(3,5-dichloropyridine-2-yl)-and 3-difluoroethoxy-4-chlorine pyrazoles-5-formic acid 17.10g, yield 91%.
(4) compound 12 is synthetic:
In the there-necked flask of 100mL, add 0.02mol (4.12g) 3 respectively, 5-two chloro-o-amino benzoic acids and 0.02mol (7.45g) 1-(3,5-dichloropyridine-2-yl)-and 3-difluoroethoxy-4-chlorine pyrazoles-5-formic acid, add the 50mL acetonitrile, stir adding 0.088mol (8.89g) triethylamine under the ice-water bath, dropwise, stir 10min, slowly drip Methanesulfonyl chloride 0.044mol (4.58g) then, reaction 4h, reaction finishes, suction filtration obtains yellow solid, washing, solid transfer is added the 50mL acetonitrile in the 100mL there-necked flask, drip 0.04mol (2.36g) Isopropylamine, reaction 1h, reaction finishes and steams solvent, obtain compound 12 product 8.06g, yield 67%.
Can prepare other compounds in the general formula I of the present invention according to above method.
The nuclear magnetic data of part of compounds is as follows:
Compound 1:
1H NMR (500MHz, DMSO): δ/ppm2.135 (s, 3H), 2.680-2.699 (d, 3H), and 4.555-4.620 (m, 2H), 6.440 (t, 1H), and 7.377-7.381 (d, 1H), 7.474 (d, 1H), 7.569-7.594 (q, 1H) .8.173-8.189 (d, 1H), 8.376-8.385 (d, 1H), 8.452-8.461 (d, 1H), 10.326 (s, 1H);
Compound 2:
1H NMR (500MHz, DMSO): δ/ppm1.084-1.095 (d, 6H), 2.132 (s, 3H), 3.949 (s, 1H), 4.557-4.615 (t, 2H), 6.330-6.545 (t, 1H), 7.193 (s, 1H), 7.308 (s, 1H), 7.365 (s, 1H), 7.579 (s, 1H), 7.698 (s, 1H), 7.739 (s, 1H), 7.920 (s, 1H), 10.222 (s, 1H);
Compound 3:
1H NMR (500MHz, DMSO): δ/ppm2.216 (s, 1H), 3.807 (s, 2H), and 4.560-4.613 (t, 2H), 5.051-5.392 (m, 2H), 5.827 (s, 1H), 6.224-6.544 (q, 1H), 7.411-7.581 (t.3H), 7.935 (s, 1H), 8.170 (s, 1H), 8.455 (s, 1H), 8.642 (s, 1H), 10.235 (s, 1H);
Compound 4:
1H NMR (500MHz, DMSO): δ/ppm1.069-1.082 (d, 6H) 6,3.919-3.933 (d, 1H), and 4.556-4.610 (q, 2H), 6.434 (t, 1H), and 7.505-7.510 (d, 1H), 7.569-7.595 (t, 1H) .7.824-7.828 (d, 1H), 8.159-8.175 (d, 1H), 8.345-8.360 (d, 1H), 8.458-8.465 (d, 1H), 10.175 (s, 1H);
Compound 5:
1H NMR (500MHz, DMSO): δ/ppm2.692-2.701 (d, 3H), 4.553-4.619 (m, 2H), 6.430 (t, 1H), 7.503-7.512 (d, 1H), 7.570-7.593 (q, 1H), and 7.825-7.829 (d, 1H), 8.261-8.274 (d, 1H), 8.460-8.469 (d, 1H), 10.212 (s, 1H);
Compound 6:
1H NMR (500MHz, DMSO): δ/ppm3.810 (s, 2H), 4.561-4.615 (t, 2H), and 5.055-5.390 (m, 2H), 5.828 (s, 1H), 6.436 (t, 1H), 7.418 (s, 1H), 7.493 (s, 1H), 8.175 (s, 1H), 8.456 (s, 1H), 8.648 (s, 1H), 10.311 (s, 1H);
Compound 7:
1H NMR (500MHz, DMSO): δ/ppm2.682-2.692 (d, 3H), 4.551-4.611 (m, 2H), 6.436 (t, 1H), 7.566-7.591 (q, 1H), and 7.670-7.673 (d, 1H), 8.058 (s, 1H), and 8.162-8.177 (d, 1H), 8.348-8.357 (d, 1H), 8.469-8.477 (d, 1H), 10.268 (s, 1H);
Compound 8:
1H NMR (500MHz, DMSO): δ/ppm2.690-2.700 (d, 3H), 4.550-4.617 (m, 2H), 6.432 (t, 1H), 7.501-7.511 (d, 1H), 7.569-7.590 (q, 1H), and 7.823-7.830 (d, 1H), 8.260-8.272 (d, 1H), 8.472-8.481 (d, 1H), 10.191 (s, 1H);
Compound 9:
1H NMR (500MHz, DMSO): δ/ppm1.070-1.083 (d, 6H), 3.917-3.930 (d, 1H), and 4.554-4.612 (q, 2H), 6.433 (t, 1H), and 7.502-7.510 (d, 1H), 7.567-7.589 (q, 1H), and 7.822-7.832 (d, 1H), 8.258-8.271 (d, 1H), 8.470-8.483 (d, 1H), 10.195 (s, 1H);
Compound 10:
1H NMR (500MHz, DMSO): δ/ppm2.137 (s, 3H), 2.682-2.694 (d.3H), 4.558-4.623 (m, 2H), 6.441 (t, 1H), 7.378-7.385 (d, 1H), 7.475-7.484 (d, 1H), and 7.571-7.597 (q, 1H), 8.175-8.192 (d, 1H), 8.455-8.467 (d, 1H), 10.321 (s, 1H);
Compound 11:
1H NMR (500MHz, DMSO): δ/ppm1.071-1.083 (s, 9H), 2.661-2.670 (d, 3H), and 4.556-4.621 (m, 2H), 6.440 (t, 1H), and 7.376-7.380 (d, 1H), 7.473-7.483 (d, 1H), and 7.567-7.592 (s, 1H), 8.172-8.187 (d, 1H), and 8.374-8.383 (d, 1H), 8.450-8.459 (d, 1H), 10.320 (s, 1H);
Compound 12:
1H NMR (500MHz, DMSO): δ/ppm1.070-1.083 (d, 6H), 3.921-3.936 (d, 1H), and 4.557-4.612 (q, 2H), 6.344 (t, 1H), and 7.509-7.515 (d, 1H), 7.572-7.601 (t, 1H), and 7.823-7.829 (d, 1H), 8.160-8.177 (d, 1H), and 8.460-8.465 (d, 1H), 10,214 (s, 1H);
Biological activity determination:
Example 4. insecticidal activity assays
Part of compounds of the present invention is to the small cabbage moth determination of activity:
Adopt leaf dipping method.The leaf dipping method that adopts international resistance Action Committee (IRAC) to propose.With the soup to be measured for preparing, with straight peen ophthalmology tweezers dipping cabbage leaves, time 3-5 gets rid of totally 3 in each 1 each sample of surplus liquid second, and peace sample flag sequence is successively placed on the treatment paper.After treating that soup is done, put into the long straight type pipe of 10cm with mark, insert 2 age 30 of diamondback moth larvaes, build the mouth of pipe with gauze.To test to handle placing in the standard treatment chamber, the 48h check result is touched polypide to pull out pin, and motionless person is dead.Calculate mortality ratio.(3 repetitions are done in test, average)
In the part test compound, following compounds is better to the preventive effect of small cabbage moth when concentration 1ppm, and mortality ratio is more than 90%: 1,2,3,4,5,6,8,10,11; In the part test compound, following compounds is better to the small cabbage moth preventive effect when 0.1ppm, and mortality ratio is more than 90%: 1,2,5,7,11; According to above method, choose compound 1, known compound KC and kill the active replicate(determination) of small cabbage moth.Test-results sees Table 2.
Table 2 kills small cabbage moth determination of activity table
By table 2 presentation of results, The compounds of this invention is compared with known compound KC small cabbage moth higher biological activity.
Claims (3)
1. 3-difluoroethoxy-4-chlorine pyrazol acid amide compounds, structure is shown in general formula I:
In the formula: R
1Be selected from methyl, Cl or Br;
R
2Be selected from Cl or Br;
R
3Be selected from methyl, sec.-propyl, the tertiary butyl, allyl group;
R
4Be selected from H or Cl.
2. the purposes of a kind of 3-difluoroethoxy according to claim 1-4-chlorine pyrazol acid amide compounds is characterized in that the single use of formula I compound or is used in combination with other bioactive compounds, and agricultural or forestry pest are had prevention effect.
3. insect-killing composition contains the described compound of Formula I of claim 1 and is acceptable carrier in active ingredient and agricultural, the forestry.
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| CN103755700A (en) * | 2013-12-26 | 2014-04-30 | 青岛科技大学 | Novel pyrazol amides compound and application thereof |
| CN106083814A (en) * | 2016-06-23 | 2016-11-09 | 浙江工业大学 | A kind of substituted pyridine connection pyrazoles acetamides and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1541063A (en) * | 2001-08-13 | 2004-10-27 | ��Ļ���Ű˾ | Method for controlling particular insects by applying anthranilamide compounds |
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| CN1541063A (en) * | 2001-08-13 | 2004-10-27 | ��Ļ���Ű˾ | Method for controlling particular insects by applying anthranilamide compounds |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103755700A (en) * | 2013-12-26 | 2014-04-30 | 青岛科技大学 | Novel pyrazol amides compound and application thereof |
| CN103755700B (en) * | 2013-12-26 | 2015-07-29 | 青岛科技大学 | A kind of pyrazol acid amide compounds and uses thereof |
| CN106083814A (en) * | 2016-06-23 | 2016-11-09 | 浙江工业大学 | A kind of substituted pyridine connection pyrazoles acetamides and its preparation method and application |
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